Substituted thiuram polysulphides and process of making the same



Patented Aug. 21, 1928.

UNITED STATES PATENT OFFICE.

GEORGE STAFFORD WHITIBY, OF MONTREAL, QUEBEC, CANADA, ASSIGNOR TO THE ROESSLER & HASSLACHER CHEMICAL 00., OF NEW YORK, N. Y., A CORPORATION OF NEW YORK.

SUBSTITUTED THIURAM POLYSULPHIDES AND PROCESS OF MAKING THE SAME.

No Drawing.

The object of this invention is the preparation of new and useful compositions of matter by the treatment of salts of dithiocarba'mic acids with sulphur chlorides. More particularly this invention relates to the products formed by treating the ,salts of substituted dithiocarbamic acids with sulphur monochloride or sulphur dichloride.

I have found that the substances so formed may be used as accelerators of the vulcanization of rubber. This use is claimed by me in a copending application S. N. 84,154, filed by me of even date herewith.

Throughout the specification I refer to specific sulphur chlorides as sulphur monochloride and sulphur dichloride giving formulas corresponding respectively to S Cl and S01 I do not wish to be limited in this since there is some doubt as to the existence or structure of the dichloride. However, I have found that by using the commonly called dichloride I obtain a definite compound of the same class as, but

differing from, the product obtained by us-.

ing' the monochloride. Furthermore, sulphur is very soluble in these sulphur chlorides and may be present in molecules of a polysulphide nature having several loosely bound S atoms in addition to those ascribed If, for example, ammonium phenyl ethyl dithiocarbamate is treated with sulphur or if sulphur dichloride is used sented as S S or S, is unknown to me. I

have, however, found that definite compositions are always formed as is shown by the properties of the various products The CoHa Application filed January 27, 1926., Serial No. 84,153.

to them by the formulae. I therefore prefer to express the sulphur chlorides above referred to as S CI wherein .1: represents a whole number other than zero.

The dithiocarbamates used in my processes are represented by the general formula:

R a s wherein R and R are any similar or dissimilar organic radicals and M is any metallic radical or equivalent group, such as zinc, sodium, potassiumor ammonium, etc. The above, as will be seen, are disubstituted dithiocarbamates. I wish it understood that in case a piperidylor any other bivalent radical is used, R and R, will be- I come a single radical utilizing the double bond, but the dithiocarbamate will still be considered disubstituted.

I have discovered that ifsuch a salt is treated with a sulphur chloride a reaction takes place between two moles of the dithiocarbamate and one mole of the sulphur chloride to form a new composition of matter. Substantially, I believe this reaction to be as follows:

monochloride a reaction takes place which I represent as follows:

products are simply named as substituted thiurampolysulphides.

I have prepared analogous materials from several dithiocarbamatcs and find the reaction similar in all cases. I have employed the dimethyl-, 'diethyl-, dibutyl-, dipropyl-, piperidylphenyl methyl-, phenyl ethyl-, dithiocarbamates. I have used zinc, sodium The following examples will serve to il-- lustrate the methods of preparation that I have used:

I Di-phenylethyl-tkiurmn tetmswlpfiz'de.

338 grams of dry ammonium phenylethyl-dithiocarbamate were suspended in petroleum naphtha, cooled with ice, and 107 grams sulphur monochloride (S 01 diluted with petroleum naphtha was run in gradually from a dropping funnel while stirring the mixture. The precipitate was filtered off, Washed with naphtha allowed to dry, suspended in water filtered, washed with water and dried. 276.5 grams of dry product were obtained; this amounts to a 76.7% yield. The melting point of the material was 142 C. After recrystallization from carbon disulphide the material analyzed 41.75% sulphur; after recrystallization from toluene it analyzed 41.25%.

35 grams well powdered amonium phenyl methyl dithiocarbamate suspended in about 200 ccs. petroleum ether cooled with ice was treated with 5.3 ccs. SCI diluted with petroleum ether; the precipitate was filtered off and washed with petroleum ether, then washed with water. Product dried ave 21.5 grams of a pale yellow powder. ield 62.1%; melting point 133 C.

l I I Di-phenylmethyl thiuram tet'rasilllphz'de.

20 grams sodium phenylmethyl dithiocarbamate were treated in ether with 6.6 grams sulphur monochloride. Washed with ether to remove excess of sulphur monochloride, then dried and suspend ed in water to remove sodium chloride and any unreacted dithiocarbamate. The product was filtered, washed on the filter with water, alcohol and ether, and finally dried. Melting point about 117 C. Product was completely soluble in corbon disulphide, and no sulphur was thrown down when acetone was added; slightly soluble in alcohol. Recrystallized from hot 95% alcohol gave a product which analyzed 55 to 57% S.

What I claim is:

1. A process for the preparation of a composition of matter consisting in reacting an ammonium salt of a substituted dithiocarbamic acid with a chloride of sulphur cor- The residue was responding to the general formula S Cl, wherein m represents a whole number other than zero. 2. A process for the preparation of a composition of matter consisting in reacting a salt of a disubstituted dithiocarbamic acid with a chloride of sulphur corresponding to the general formula S Cl wherein as represents a whole number other than zero.

3. A process for the preparation of a composition of matter consisting in reacting a salt of a phenyl ethyl dithiocarbamic acid with a chloride of sulphur corresponding to the general formula S Cl wherein a: represents a whole number other than zero.

4. A process for the preparation of a composition of matter consisting in reacting the ammonium salt of a phenyl ethyl dithiocarbamic acid with sulphur monochloride.

5. A composition of matter comprising diphenyl-diethyl thiuram tetrasulphide.

. 6. A composition of matter comprising an organic compound having as its nucleus a radical corresponding to the formula wherein 00 represents a whole number other than zero.

7. A composition of matter comprising an organic compound having as its nucleus a radical corresponding to the formula 8. A composition of matter comprising a tetra-substituted organic compound having as its nucleus a radial corresponding to the formula wherein m represents a whole number other than zero.

9. A composition of matter-comprising a dialkyl-diaryl substiuted organic compound having as its nucleus a radical corresponding to the formula Ill 

